Elucidation of the electronic structure of molecules with the help of NMR spin-spin coupling constants

the FH molecule

Jürgen Gräfenstein, Tell Tuttle, Dieter Cremer

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

It is demonstrated how the one-bond NMR spin-spin coupling constant (SSCC) 1J(FH) can be used as a source of information on the electronic structure of the FH molecule. For this purpose, the best possible agreement between measured and calculated SSCC is achieved by large basis set coupled perturbed density functional theory calculations. Then, the calculated value is dissected into its four Ramsey terms: Fermi contact, the paramagnetic spin-orbit term, the diamagnetic spin-orbit term, and the spin dipole term, which in turn are decomposed into orbital contributions and then described by their spin densities and orbital current densities. In this way, the SSCC gives detailed information about the electronegativity of F, the bond polarity, the bond polarizability, the volume and the polarizability of σ and π lone pair orbitals, the s- or p-character of the bond orbital, the nature of the LUMO, and the density distribution around F.

Original languageEnglish
Pages (from-to)2325-2339
Number of pages15
JournalJournal of Physical Chemistry A
Volume109
Issue number10
Early online date22 Feb 2005
DOIs
Publication statusPublished - 17 Mar 2005

Fingerprint

spin-spin coupling
Electronic structure
Orbits
Nuclear magnetic resonance
electronic structure
orbitals
Electronegativity
nuclear magnetic resonance
Molecules
Density functional theory
molecules
Current density
orbits
density distribution
electric contacts
polarity
current density
dipoles
density functional theory

Keywords

  • spin-spin coupling constants
  • SSCCs
  • FH molecule
  • Fermi contact spin coupling

Cite this

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abstract = "It is demonstrated how the one-bond NMR spin-spin coupling constant (SSCC) 1J(FH) can be used as a source of information on the electronic structure of the FH molecule. For this purpose, the best possible agreement between measured and calculated SSCC is achieved by large basis set coupled perturbed density functional theory calculations. Then, the calculated value is dissected into its four Ramsey terms: Fermi contact, the paramagnetic spin-orbit term, the diamagnetic spin-orbit term, and the spin dipole term, which in turn are decomposed into orbital contributions and then described by their spin densities and orbital current densities. In this way, the SSCC gives detailed information about the electronegativity of F, the bond polarity, the bond polarizability, the volume and the polarizability of σ and π lone pair orbitals, the s- or p-character of the bond orbital, the nature of the LUMO, and the density distribution around F.",
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Elucidation of the electronic structure of molecules with the help of NMR spin-spin coupling constants : the FH molecule. / Gräfenstein, Jürgen; Tuttle, Tell; Cremer, Dieter.

In: Journal of Physical Chemistry A, Vol. 109, No. 10, 17.03.2005, p. 2325-2339.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Elucidation of the electronic structure of molecules with the help of NMR spin-spin coupling constants

T2 - the FH molecule

AU - Gräfenstein, Jürgen

AU - Tuttle, Tell

AU - Cremer, Dieter

PY - 2005/3/17

Y1 - 2005/3/17

N2 - It is demonstrated how the one-bond NMR spin-spin coupling constant (SSCC) 1J(FH) can be used as a source of information on the electronic structure of the FH molecule. For this purpose, the best possible agreement between measured and calculated SSCC is achieved by large basis set coupled perturbed density functional theory calculations. Then, the calculated value is dissected into its four Ramsey terms: Fermi contact, the paramagnetic spin-orbit term, the diamagnetic spin-orbit term, and the spin dipole term, which in turn are decomposed into orbital contributions and then described by their spin densities and orbital current densities. In this way, the SSCC gives detailed information about the electronegativity of F, the bond polarity, the bond polarizability, the volume and the polarizability of σ and π lone pair orbitals, the s- or p-character of the bond orbital, the nature of the LUMO, and the density distribution around F.

AB - It is demonstrated how the one-bond NMR spin-spin coupling constant (SSCC) 1J(FH) can be used as a source of information on the electronic structure of the FH molecule. For this purpose, the best possible agreement between measured and calculated SSCC is achieved by large basis set coupled perturbed density functional theory calculations. Then, the calculated value is dissected into its four Ramsey terms: Fermi contact, the paramagnetic spin-orbit term, the diamagnetic spin-orbit term, and the spin dipole term, which in turn are decomposed into orbital contributions and then described by their spin densities and orbital current densities. In this way, the SSCC gives detailed information about the electronegativity of F, the bond polarity, the bond polarizability, the volume and the polarizability of σ and π lone pair orbitals, the s- or p-character of the bond orbital, the nature of the LUMO, and the density distribution around F.

KW - spin-spin coupling constants

KW - SSCCs

KW - FH molecule

KW - Fermi contact spin coupling

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